Scholarly Works (5 results)

The gas-phase reaction of benzene with O(3P) is of considerable interest for modeling of aromatic oxidation, and also because there exist fundamental questions concerning the prominence of intersystem crossing in the reaction. While its overall rate constant has been studied extensively, there are still significant uncertainties in the product distribution. The reaction proceeds mainly through the addition of the O atom to benzene, forming an initial triplet diradical adduct, which can either dissociate to form the phenoxy radical and H atom, or undergo intersystem crossing onto a singlet surface, followed by a multiplicity of internal isomerizations, leading to several possible reaction products. In this work, we examined the product branching ratios of the reaction between benzene and O(3P) over the temperature range of 300 to 1000 K and pressure range of 1 to 10 Torr. The reactions were initiated by pulsed-laser photolysis of NO2 in the presence of benzene and helium buffer in a slow-flow reactor, and reaction products were identified by using the multiplexed chemical kinetics photoionization mass spectrometer operating at the Advanced Light Source (ALS) of Lawrence Berkeley National Laboratory. Phenol and phenoxy radical were detected and quantified. Cyclopentadiene and cyclopentadienyl radical were directly identified for the first time. Finally, ab initio calculations and master equation/RRKM modeling were used to reproduce the experimental branching ratios, yielding pressure-dependent rate expressions for the reaction channels, including phenoxy + H, phenol, cyclopentadiene + CO, which are proposed for kinetic modeling of benzene oxidation.

Deer-vehicle collisions are on the rise and are a costly side-effect of increasing deer populations and expanding transportation systems. We evaluated the efficacy of sound as a deterrent for reducing deer-vehicle collisions by observing the behavioral response of captive and free-ranging white-tailed deer (Odocoileus virginianus) to 5 pure-tone sound treatments: 0.28 kHz, 1 kHz, 8 kHz, 15 kHz, and 28 kHz. We conducted preliminary trials with semi-tame deer at the University of Georgia Captive Deer Research Facility. We exposed 8 deer in a 0.25-ha outside paddock and 5 deer in individual stalls (2.7 m x 4.8 m) to the various treatments at >70 dB Sound Pressure Level. We recorded 406 observations and determined that the behavior of captive deer did not change when presented with any of the 5 pure-tone sound treatments. We also conducted field trials at Berry College Wildlife Refuge, Georgia and gathered 319 behavioral observations of free-ranging deer relative to a moving automobile (56.45 kph). The automobile was fitted with a sound-producing device and speakers that emitted one of the pure-tone sound treatments or no sound treatment as a control. For the 1 kHz, 8 kHz, 15 kHz, and 28 kHz sound treatments, we observed no change in deer behavior relative to the control. When exposed to the 0.28 kHz treatment, deer reacted in a manner more likely to cause deer-vehicle collisions. Our results indicate that deer within 10 m of roadways did not alter their behavior in response to the pure-tone sound treatments we tested in a manner that would prevent deer-vehicle collisions. Commercially available wildlife warning whistles (aka deer whistles) are purported to emit similar consistent, continuous sounds as pure tones at various frequencies within the range of those presented in this study. Our data suggests that deer-whistles, as they are purported to operate, are likely not effective in preventing deer-vehicle collisions.

The products formed in the reaction between the methylidene radical (CH) and acrolein (CH2═CHCHO) are probed at 4 Torr and 298 K employing tunable vacuum-ultraviolet synchrotron light and multiplexed photoionization mass-spectrometry. The data suggest a principal exit channel of H loss from the adduct to yield C4H4O, accounting for (78 ± 10)% of the products. Examination of the photoionization spectra measured upon reaction of both CH and CD with acrolein reveals that the isomeric composition of the C4H4O product is (60 ± 12)% 1,3-butadienal and (17 ± 10)% furan. The remaining 23% of the possible C4H4O products cannot be accurately distinguished without more reliable photoionization spectra of the possible product isomers but most likely involves oxygenated butyne species. In addition, C2H2O and C3H4 are detected, which account for (14 ± 10)% and (8 +10, -8)% of the products, respectively. The C2H2O photoionization spectrum matches that of ketene and the C3H4 signal is composed of (24 ± 14)% allene and (76 ± 22)% propyne, with an upper limit of 8% placed on the cyclopropene contribution. The reactive potential energy surface is also investigated computationally, and specific rate coefficients are calculated with RRKM theory. These calculations predict overall branching fractions for 1,3-butadienal and furan of 27% and 12%, respectively, in agreement with the experimental results. In contrast, the calculations predict a prominent CO + 2-methylvinyl product channel that is at most a minor channel according to the experimental results. Studies with the CD radical strongly suggest that the title reaction proceeds predominantly via cycloaddition of the radical onto the C═O bond of acrolein, with cycloaddition to the C═C bond being the second most probable reactive mechanism.